Metalliferous disazo-dyestuffs and process of making same



Patented Nov. 21, 1933 UlTED carers METALLIFEROUS DISAZG-DYESTUFFS AND PEGCESS @F MAKING SAME Switzerland No Drawing.

Application February Se ial 856,628, and in Switzerland February 18, 1932 19 Claims. (Cl. 26ll--l2) The present invention relates to new disazodyestuffs. It comprises the process of making these dyestuffs, the dyesturls themselves and the material dyed with the new dyestuffs.

According to the present invention new valuable metalliferous disazodyestufis may be ob tained as iollows2-Treating the lz l dinitro stilbene-B:3-dicarhoxylic acid in a step with reducing agents, such as for example iron or zinc, or with alkali sulfides, such as for example sodium sulfide, tetrazotizlng the lzQ-diazninostilhene-B:3dicarboxylic acid thus obtained in a second step with nitrous coupling the tetrazotized l: l-diamimostilhene-3:3- dicarboxylic acid in a third step with coupling components, and finally treating the disazo-dyestuffs of the general formula wherein R and R1 represent the radicles of coupling components, in a fourth step with an agent yielding metal capable of forming lakes with the lake forming groups of the disazo-dyestuffs.

Coupling components which may be coupled with the tetraaotized 4:4'-dianiinosti1bene-3:3- dicarboxylic acid are all those which come into consideration for the production of azo-dyestuffs, such as for example arylaniines, phenols, naphthols, as Well as their substitution products which may contain for example halogemsulfonic acid groups, alky1-, nitroor alkoXy-groups, as also compounds of which the carbon atom capable of coupling belongs to a heterocyclic ring or to an open chain. The former is for example the case with pyrazolones, hydroxyquinolines and carbituric acids, as Well as with their substitution productswhich may contain for example halogen, -sulfonic groups, alkyl-, nitro-, or alkoxygroups; the latter for instance with the acetoacetic acid derivatives and the benzoylaceto-ocarboxylic acids.

As agents yielding ii etal capable of forming lakes with the lake-forming-groups of the disazo-dyestuff there come into consideration for example compounds of chromium, copper, iron, cobalt, nickel, manganesazinc, vanadium, and titanium. Of these particularly valuable results are obtained Withthose which contain metals of the atomic weight 52 to 66, and the most valuable dyestuffs are obtained with agents yielding copper.

The disazo-dyestufis may he treated with the agents that yield metal either in substance or on the fiber or in the dye-hath; the treatment can also occur simultaneously with the production of the azo-dyestufi.

The metalliierous dyestuffs thus obtained may contain one or more metals; in making those that have more than one metal, the agents that yield the metals may be used simultaneously or in succession in forming the metalliferous dyestuff.

The treatment with the agent that yields metal may he in acid, neutral or alkaline medium, with or without a suitable addition and at normal or raised pressure.

The complex metal compounds made in accordance with the invention may be used for dyeing materials of any kind, such as cotton, wool, loaded or non-loaded silk, leather, artificial silk from regenerated cellulose, cellulose esters or ethers, or varnishes made from a cellulose oasis and a natural or artificial resin basis; or as pigments or in printin The dyeings are of various tints and are very fast.

The following examples illustrate the invention, the parts being by weight:

Example 1 17.9 parts of l: i-dinitrostilone-3:3' dicarylic acid are dissolved in 106 parts of hot the ads tion of 13 parts of caustic soda solution of 30 per cent. strength and, after addition a solution of 43 parts of crystal ed sodium sulfide in 120 parts of water, the who is heate to coiling for some minutes and then stirred for about an hour at 80 C. The mass is acidified, while not, with dilute hydrochloric acid, then allowed to cool, neutralized by means of sodium acetate until it imparts a very feeble blue to Congo paper, and then filtered. For the separation of sulfur the prod- .uct reprecipitated from its solution in sodium carbonate or dilute caustic soda solution, The

4 4 -diaminostilbene 3 :3 dicarboxylic acid of the formula lTTHs thus obtained is a yellow to reddish-brown powder.

The 4:4 dinitrostilbene 3:3 dicarboxylic acid, which is the parent material in this example, may be made from 6-nitro-3-methyl-1- benzoic acid by oxidation with sodium hypochlorite in an alkaline solution. It is a greenish-yellow powder, very sparingly soluble in water; after recrystallization from boiling nitrobenzene it melts above 280 C.

Example 2 29.8 parts of 4: i'-diaminostilbene-3:3'-di carboxylic acid are suspended in 360 parts of water and dissolved by addition of the proportion of caustic soda solution necessary for forming the di-sodium salt. To the neutral or feebly alkaline solution there are added 14 parts of sodium nitrite in the form of an aqueoussolution of 2s per cent. strength and the whole is stirred well, while there is gradually run in a mixture of 70 parts of concentrated hydrochloric acid and ice. After stirring for some time the tetrazo solution assumes a light brown color. It is then run. into a cooled solution, alkaline with sodium carbonate, of 48 parts of 1-amino-8-hydroxynaphthalene--sulfonic acid. When coupling is complete the dyestufi of the formula is filtered after addition of some common salt; if desired it may be re-precipitated and dried. It is a dark powder, soluble in concentrated sulfuric acid to a blue solution and in water to a violet solution. It dyes cotton in neutral or feebly alkaline baths grey-blue tints which become fast green-blue when treated with copper salts.

Example 3 Into the solution of the tetrazotized 4:4-diamino-stilb'ene 3:3 dicarboxylic acid, made as described in Example 2, there is poured while stirring well a cooled solution, alkaline with sodium carbonate, of 22.4 parts of l-hydroxynaphthalene--suifonic acid. When coupling is complete there is added a solution, alkaline with sodium carbonate, of 31.5 parts of 2-(phenyl)- amino 5 hydroxynaphthalenefl -sulfonic acid. Towards the end of the coupling the mass is gently warmed. The dyestufi of the formula is now filtered, after addition of common salt, and if desired recrystallized and dried. It is a dark powder of bronze lustre, which dissolves in concentrated sulfuric acid to a blue solution and in water to a red-violet solution; it dyes unmordanted cotton reddish-violet, which by subsequent treatment with copper salts passes into a fast pure violet.

Example 4 Into the solution of the tetrazotized 4:4- diaminostilbene-3 :3 -dicarboxylic acid obtained as described in Example 2 is poured, while stirring well, a cooled solution, alkaline with sodium carbonate, of 24 parts of 1.-amino-8-hydroxynaph thalenei-sulfonic acid. The formation of the intermediate dyestuff comes rapidly to an end.

There is then added an alkaline solution of 19.2 parts of acetic acid anilide and the Whole is heated somewhat towards the end of the coupling. After salting out, filtering and drying, the dyestufi of the formula is a dark powder which dissolves in concentrated sulfuric acid to a muddy violet solution and in water to a claret-red solution, and dyes cotton brownish-grey tints which become a very fast olive by subsequent treatment with copper salts.

Example 5 Into the solution of the tetrazotized 4:4- diaminostilbene-S :3 -dicarboxylic acid, obtained as described in Example 2, there is run a cooled solution, alkaline with sodium carbonate, oi 63..

parts of Z-(phenyl)-amino-hydroXynaphthalene-7-sulfonic acid. Stirring is continued, while cooling with ice, and subsequently at room temperatiu'e', until a test sample in concentrated sul- 5 furic acid shows no further change of color. The mass is then feebly heated for some time. The salted-out dyestuff of the formula is re-precipitated and dried. It is a dark powder of bronze lustre which dissolves in concentrated sulfuric acid to a blue solution, in water to a red-violet solution and produces on unrnordanted cotton a violet tint, which, when subsequently treated with copper salt, passes into a fast, pure blue-violet.

Example 6 10 parts of the dyestulf obtainable as described in Example 5 are dissolved in 5000 parts of hot water and, after addition of some ammonia, the solution is heated for a solution of ammoniacal copper oxide corresponding with 5 parts or" crystallized copper sulfate. After neutralizing with acetic acid the dyestuff is salted out completely and filtered. When dry it is a dark powder of bronze lustre, soluble in water to a violet solution and dyeing cotton in a bath containing Glaubers salt pure blueviolet tints.

Example 7 To the solution of the tetrazotized 4:4'-diaminostilbene-S:3-dicarboxylic acid made as dering well, a solution, made alkaline with sodium bicarbonate, of 28.8 parts of 1-(2-chloro-5-sulfophenyl)-3-methyl-5-pyrazolone and, when the formation of the intermediate dyestuff is complete, an alkaline solution of 17.4 parts of 1 coupling is complete, the dyes'tuif'of the formula N: -CC-OH3 COOH 110 1 1 l -o1 CH Hols on coon H N=N-oc-om is salted out, filtered and dried. It is a brownhour at 89-90" C. with scribed in Example 2, there is added, while stira phenyl-3-methyl-5pyrazolone is added. When red powder,.soluble in concentrated sulfuric acid to a violet solution and in water to a yellowbrown solution; it dyes cotton a covered red which yields a fast-red-orange by after-treatment with a copper salt.

' a Example 8 8 parts of the disazo-dyestuii made as described in Example 7 are dissolved in 2400 parts of hot water and, after addition of a solution of 6 parts of crystallized copper sulfate in 50 parts of water, the mixture is heated for 2 hours at Til- C. The dye'stuif is then completely precipitated by addition of common salt, filtered and dried. The cupriferous dyestuff is a reddish-brown powder which dissolves in water to an orange brownish solution. By concentrated sulfuric acid the metal compound is immediately split up. On cotton, in a bath containing Glaubers salt, the dyestufi produces a fast reddish-orange which corresponds completely in shade with that produced on the fiber by after-treatment of the dyestuff made according to Example '7.

Example 9 COOH HN 15 r CH .121) (|)H 11TH: @0011 SOaH is filtered after addition of some common salt.

,After drying a dark powder is obtained dissolving in water to a blue-violet solution, and in concentrated sulfuric acid to a muddy violet solu-' tion. It dyes cotton in a bath containing Glaubers salt blue-violet tints which become blue by subsequent treatment with copper salts. I

3.5 parts of this dyestufi are dissolved in 1500 parts or" hot water and after addition of 2.5 parts of ammonia combined with vanadic acid boiled for 2 hours in a reflux apparatus. The dyestuff is then precipitated and filtered by addition of .1 common salt. After drying it is a dark powder, dissolving in concentrated sulfuric acid to a blue solution, and in water to a violet solution, and

dyeing cotton in a bath containing Glaubers salt violet tints.

Example 10 A solutionoi the tetrazotized 4:4-diaminostilbene-S:3-dicarbo;ylic acid is made as described in Example 2. To the tetrazo solution 150 there is added, while stirring well, a solution of continued, at the beginning while cooling with dition of an ammoniacal solution of 7.2 parts of nickel-sulfate heated for 2 hours to 90 C. The dyestuff is then precipitated and filtered by addition of common salt. After drying it is a ice, and subsequently at room temperature, until dark powder of bronze lustre, dissolving in con- 8 the coupling is complete. The dyestuif of the centrated sulfuric acid to a blue solution, and formula, dyeing cotton in a bath containing Glaubers salt violet tints. (1)0133 Example 11 E038 7.5 parts of the dyestuff obtained according to Example '7 are dissolved in 750 parts of hot N Water and after addition of a chromium fluoride OOOH solution corresponding to 1.52 parts of CrzOz 6 boiled for a long time in a reflux apparatus. The

dyestufi is then precipitated and filtered by addition of common salt. After drying it'is a redbrown powder dissolving in concentrated sulfuric acid to a red-violet solution and in water to a red-brown solution, and dyeing cotton in a 295 bath containing Glaubers salt reddish tints.

OH Example 12 OOOH A dye-bath is prepared with 2 parts of the N N CCH: dyestuif of'Example '7, 50 parts of Glaubers salt 0 or 30 parts of common salt. parts of cot- 10 H035 G ton are introduced into the bath at 60-70 C. the temperature is raised to the boil within hour, is filtered off after addition of some common salt, and dyeing is continued for A2 to hour. The ifnecessary re-precipitated and dried. goods are then rinsed and after-treated for 1 It represents a dark powder of bronze lustre hour in afresh bath at 60-70 C. after addition dissolving in concentrated sulfuric acid to a blue of 2 parts of chromium formate. Subsequently solution, in water to a violet solution, and dyethe goods are rinsed and dried. Cotton is dyed :ing cotton violet tints which become blue-vioreddish tints. let by subsequent treatment with copper salts. In the following table are given the proper- 11 parts of this dyestufi are dissolved or susties of some of the cupriferous dyestuffs obtainno pended in 2000 parts of hot water and after adable according to this invention:--

Dyeing on Coupling component Formula of the disnzo-dyestuff 532 33 33 ous dyestuil 1 2 mol. 2-(phenyl)-amino-8-hydroxyhaph- 0H .Reddishthalene-fi-sulionic acid grey.

COOH

' Hols COOH e N 0 on 1 (2) 1 mol. l-amino-S-hydroxynaphthalene-- OH NH: Green-grey.

sulfonic acid and 1 mol. barbituric acid 1 COOH Mt I S OaH i OH 132 COOH C NH\ N=N--C o0 CO-NH Coupling component Formula of the disazo-dyestufi Dyeing on cotton with the cupriferous dyestufi (11) 1 mol. 2-(phenyl)-amin0naphthalene and l N i Violet.

mol. 1-hydroxynaphthalene-fi-sulfonic acid. COOH EN O 85 H II CH COOH OaH

:9 (12) lmol. 2-(phenyl)-amino-8-hydroxynaphthalene-S-sulfonic acid and 1 mol. 2-(phenyl) ami110-5-hydroxynaphthalene-7-sulionic acid.

(13) 2 mol.7'-su1io-5-hydrow-2-naphthyl-4- aminophenoxy-acetic acid.

B0 (14) 111101. 2-(pheny1) -amino-5-hyclroxynaphthalene-T-sulfonic acid and 1 mol. l--amino-8- hydroxynaphthalene-i-sullonic acid.

(RH IITHz l SOaH Blue violet.

Blue.

Reddish blue.

ti "it co on W1 Coupling component Formula of the disazo-dyestufi the cupriferous dyestufi (15) lmol. 2-(phenyl)-amino-naphthalene-5:7- N N R 9. i g i S disulfonic acid and 1 mol. Z-hydroxynaphtha- O O OH HN SOaH 3 lene.

H H S O :11 OH O O OH $0 OH HOaS- --NHC (16) 2 11101. 2 (2 carboxy) phenylamino 5 N N Blue hydroxynaphthalene-7-sulfonic acid. 0 O OH tn H OH OH 0 0 OH I N=N ('30 OH HOsS- NH (RUB;

2 17) 2 mol. 2 (2 methoxy) phenylamino 5 Blue violet.

hydroxynaphthalene-i-sulfonic acid.

I (IIIIH CH OH 0 o o n HOaS NHO What we claim is:-

1. As a step in the manufacture of metalliferous disazo-dyestuffs, tetrazotizing the 4:4-diami hostilbene-B:3-dicarboxy1ic acid with nitrous acid.

2. As a step in the manufacture of metalliferous disazo-dyestufis, coupling the tetrazotized 4:4- diaminostilbene-3:3'-dicarboxy1ic acid with coupling components.

3. As a step in the manufacture of metalliferous disazo-dyestuifs, coupling the tetrazotized 4:4- diaminostilbene-3:3-dicarboxy1ic acid with coupling components of the naphthalene series.

4. As a step in the manufacture of metalliferous disazo-dyestuffs, coupling the tetrazotized 4:4- diaminosti1bene-3:3'-dicarboxy1ic acid with 2- (phenyl) amino 5 hydroxynaphthalene-7-sulfonic acid.

5. As a step in the manufacture of metalliferous disazo-clyestufis, treating the disazo-dyestufis of the general formula wherein R and R1 represent the radicles of coupling components, with an agent yielding metal capable of forming lakes with the lake-forming groups of the disazo-dyestuffs.

6. As a step in the manufacture of cupriferous disazo-dyestuffs, treating the disazo-dyestufis of the general formula the obtained disazo-dyestuffs of the general formula wherein R and R1 represent the radicles of coupling components, in a fourth step with an agent yield ng metal capable of forming lakes with the lake-forming groups of the disazo-dyestufis.

8 Process for the manufacture of cupriferous disazo-dyestuifs, consisting in treating the Q14- initrostilbene-B:3'dicarbo: ylic acid in a first step with reducing agents, tetrazotieing the 4:4- diaminostilbene-B:3 dicarhoxy1ic acid in a second step with nitrous acid, coupling the tetrazotized 4: i -diaminostilhene 3 3 -dicarboxylic acid in a third step with coupling components of the naphthalene series and treating the obtained disaZo-dycstuff of the general formula wherein R and R1 represent naphthalene radicles, in a fourth step with agents yielding copper.

9. The metalliferous disaZo-dyestuffs, which disazo-dyestuffs correspond with the general formula wherein R and R1 represent the radicles of coupling components, which products form redbrown to dark colored powders, dissolving in water to brown to orange to red to red-violet to violet solutions and dyeing cotton orange to'violet to blue to grey tints. I

10. The inetalliferous disazo-dyestufis which contain metals of the atomic weight 52 to 66, which disazo-dyestufis correspond with the general formula I wherein R and R1 represent the radicles of coupling components, which products form redbrown to dark colored powders, dissolving in water to brown to orange to red to red-violet to violet solutions and dyeing cotton orange to violet to blue to grey tints.

11. The cupriferous disazo-dyestuffs, which disazo-dyestuifs correspond with formula the general N==N-R coon ( n on coon N=N-- R 1 wherein R and R1 represent the radicl s of coupling components, which products form redbrown to dark colored powders, dissolving in water to brown to orange to red to red-violet to violet solutions and dyeing cotton orange to violet to blue to grey tints.

12. Cupriferous disazo-dyestuifs, which disazodyestuffs correspond with the general formula wherein R and R1 represent aryl radicles, which products form red-brown to dark colored powders, dissolving in water to red to red-violet to violet solutions and dyeing cotton to violet to blue to grey tints.

13. Cupriferous disazo-dyestuffs, which disazodyestuffs correspond with the general formula wherein R and R1 represent naphthalene radicles, which products form red-brown to dark colored powders, dissolving in water to red to red-violet to violet solutions and dyeing cotton violet to blue to grey tints.

14. A cupriferous disazo-dyestuff, which disazodyestuff corresponds with the formula which product forms a dark powder, dissolving in water to a violet solution and dyeing cotton blue-violet tints.

15. Cupriferous disazo-dyestuffs, which disazodyestuffs correspond with the general formula wherein R and R1 represent the radicles of such coupling components whose carbon atoms linked with the -l l N-bridges belong to heterocyclic rings, which products form red-brown to dark colored powders, dissolving in water to brown to orange to red solutions and dyeing cotton orange to brown tints.

l6. Cupriferous disazo-dyestufis, which disazodyestuffs correspond with the general formula N=N R coon ||H on coon -N=N-R1 wherein R and R1 represent the radicles of such coupling components whose carbon atoms linked with the N N-bridges belong to pyrazolone rings, which products form red-brown to dark colored powders, dissolving in water to brown to orange to red solutions and dyeing cotton orange to brown tints,

dyestufi corresponds with the formula R1 represents a radicle of such coupling component whose carbon atom linked with the --N:N-bridge belongs to an open chain, which 17. A cupriferus disazo-dyestuff, which disa-zo- -N==N--c'o-ori COOH 3 products form dark colored powders, dissolving HO O\ in Water to red solutions and dyeing cotton grey N tints.

l 19. A cupriferous disazo-dyestufi, which disazo-dyestuff corresponds with the formula 011 II on 0H NH:

N 00011 t 00011 W -N=N-C*OCH3 SOsH which product forms a red-brown powder, dis- 6 solving in water to an orange-brown solution and OH dyeing cotton red-orange tints. l

18. Cupriferous disazo-dyestuffs, which disazo- CH3 dyestuffs correspond with the general formula.

-N:NR 00011 coon --N N(l3 compo OH .105 111 which product forms a dark colored powder, dissolving in water to a red solution and dyeing cot- OOOH ton brown-grey tints.

N=NR1 FRITZ STRAUB.

wherein R represents a naphthalene radicle and WALTER HANHART. 

